Reclaiming synthetic rubbers with a fatty acid and live steam



Patented June '24, 1947 UNITED STATES,"

.ascmmumc SYNTHETIC Business wrm a) FAmAomaNnuvas-rnm My Be Vilma le Beau, Cambrian. Mam, auignor,

* by memo assignments, to Midwest Bubber Bcclaiming Company, East St. Louis, 111., a corpoi-ation of Delaware No Drawing. Application July 24, 1944, -semmamazs This application is a continuation in part of my original application, Serial No. 403,373, filed July 21, 1941. a

My present invention relates to reclaiming fully or partly vulcanized or scorched synthetic rubdoes not interfere with the operation of the process.

At the present time it is very important to be able to reclaim such rubbers.

Heretofor natural rubbers have been reclaimed by several processes, for instance, by the use of alkalies and oils at high pressures and temper-' atures; by the use of acids also under high pres- The presroams. (oi. zoo-23) I tures of the several rubbers may be simultaneously reclaimed by the same process.

Polymerized conjugated diolednes and their copolymers which will vulcanize with sulphur may also be treated "by exactly the same method.

My present invention, is based on three discoveries. First, that certain substances, when mixed with scrap of the various types already mentioned and subjected to live steam under proper conditions, have the effect of bringing the scrap back into condition in which it can be again successfully processed.

Second, that.when treated with the reclaiming substance, vulcanized neoprene becomes vullii canizable with sulphur in thesame way as are natural. or othersynthetic rubbers; that it does not lose its individual characteristics, such as resistance to oil and aging, and that it becomes compatible with. natural or other synthetic rubsures and temperatures; and to some extent by so bers with which in theunreacted state it was not digestion in rubber solvents. Attempts have also re made to bring synthetic and natural rubbers to a reworkable condition by working them mechanically for a long time with large proporcompatible. v v k Third, that suitable treating substances are (1) long chain saturated fatty acids having from 4 to 18 carbon atoms and which do not contain hytions of plasticizer, but the results have been 25 droxyl groups in the chain other than those in unsatisfactory. So far it has not been possible to reclaim synthetic rubbers of the group consisting of polymerized conjugated dioleflnes and their copolymers and chloroprene polymers successfully, much less has it been thought that any single process could be devised to reclaim the several types simultaneously, since they have different chemical and physical characteristics. As far as I have been able to ascertain, no successful and economically practical process of reclaiming such synthetic materials has been devised and it may well have been assumed that none could be.

As is well known tothose skilled in the art,

"neoprene," which is a trade name for polymeris not in general compatible in vulcanization with natural rubber or with other synthetic rubbers,

probably owing to the presence and efiect of the chlorine which it contains in its molecule. However, when vulcanized neoprene is treated in accordance with the process herein described it as resistance to oil and aging. Likewise mixthe carboxyl groups, and (2) certain organic amines described in my copending application Serial No. 471,882, filed January 9, 1943, which is a continuation of application Serial NIL-403,372, filed July 21, 1941.

The work which I have done proves conclusively that unsaturated fatty acids and short chain saturated fatty acids are ineffective. while long chain saturated fatty acids having from 4 35 to 18 carbon atoms and which do not have hydroxyl groups in the chain other than those in the carboxyl groups are eflective when used in amounts of from 3 to 35%, depending on the degree of vulcanization of the scrap to be treated.

' My present invention includes both the method of reclaiming fully or partially vulcanized or scorched synthetic materials of the kind described and the resulting product which appears to be an altogether new substance or compound. The claims of the present application are limited to the use of long chain saturated fatty acids of the kinds already mentioned and the products resuiting therefrom, while inmy said companion application Serial No. 471,882 I have claimed the method of reclaiming by the use of the organic amines defined therein and the products resulting therefrom.

When using the acids as reclaiming agents, I 11nd that itis desirable tomix-the acid with a solvent therefor, thesolvent being also capable a 3 of sw s' the scr p. and then to mix thoroug y the scrap with this solution. When this is done, the solvent may, ii desired, be evaporated from the mixture before the mixture is treated with live steam, or the solvent maybe left in the mix during the treatment. The solvent carries the acid into the material more perfectly than is the case where no solvent is used. The-tact that the reaction may be carried out eirectively after the solvent has been removed shows that the acid rather than the solvent is the active reclaiming agent.

In this application I have used the word "solvent to include those substances which are solvents of the particular acid employed and which are also capable oi swelling the material which is being processed.

My invention will be understood from the following specific examples:

The scrap is first ground into small particles such as is customary in the rubber reclaiming industry.

' Exams 1 900 grams of scrap (vulcanized neoprene scrap.

vulcanized Ameripol scrap. or vulcanized German buna scrap, or vulcanized Thiokoi, polyalkylene polysulflde, scrap) 32 grams (1. 'e. 3.55% or the weight of the scrap) of lauric acid. CH:(CI-I:)mCOOH 300 grams of solvent naphtha Mixing procedure lbs. live steam pressure. After the pressure has been released the scrap is ready for milling. It will form a sheet immediately, can be refined, recompounded and recured without any difllculties.

It may also be said that Ameripol scrap is stated to be a copolymer of butadiene and acrylic nitrile or styrene; and that German buna includes polymers of butadiene and copolymers of butadiene and styrene, and of butadiene and comic- .nitrile.

900 grams of neoprene G. N. tire scrap 32 grams (i. e. 3.55% of the weight 01' the scrap) of stearic acid, crmcmmcoon 300 grams of trichlorethylene Mixing procedure The stearic acid is dissolved in the solvent and the solution added to thescrap while stirrin the latter so that a thorough wetting of the particles is obtained. Then about 2000 grams of water are added and the whole mixture placed in a disester or autoclave. The amount of water will depend on the particular digester used for this p p se and must not only sumce to keep the scrap in a moist condition throughout the treatment but also be large enough to allow the desired pressure to be built up. In this case the scrap was subjected to a pressure of 200 lbs. during 5hours. The pressure was then released, the digester opened and the scrap washed and dried. The scrap was then ready for milling andreflning as well as recompounding and recuring.

In the following examples the scrap employed 4 and the mixing procedure were the same as has been described in connection with Example 2.

Exama3 irramsscrap 25 grams caproic acid, CsHnCOOH Treat for 9 hour with live steam at 190 lbs.

pressure.

Exams: 4 100 grams scrap 25 grams caprylic acid, C'IHISCOOH 20 grams solvent naphtha Treat for 12 hours with live steam at lbs.

Treat for 18 hours with live steam at 100 lbs.

pressure.

Exmu 6 100 grams scrap 3 grams stearic acid, CfiHssCOOH 10 grams solvent naphtha Treat for 8 hours with live steam at 200 lbs. pressure.

Exams: '7

100 grams scrap 25 grams stearic acid, CnH'isCOOH 30 grams trichlorethylene Treat for 5 hours with live steam at 200 lbs. pressure.

EXAMPLE 8 100 grams scrap 25 grams lauric-acid 20 grams solvent naphtha Treat for 5 hours with live steam at 200 lbs.

pressure.

Exlmpu: 9

100 grams scrap 3 grams lauric acid 10 grams trichlorethylene Treat for 6 hours with live steam at lbs. pressure.

Exma: 10

100 grams scrap 35 grams stearic acid 20 gram solvent naphtha Treat for 5 hours with live steam at 200 lbs.

pressure.

Exem t-z 11 100 grams scrap from a whole tire having a natural rubber carcass and a butadiene-styrene copolymer tread stock 20 grams stearic acid, CnHssCOOH 30 grams solvent naphtha while it will be understood that the usual softeners can be added during or after the reclaim.- ing process, I prefer not to do'so as it interferes with the physical properties of the final product. Likewise it will be understood that the usual fillers, accelerators and other compounding ingredientsmay be employed subsequently to the reclaiming process.

The result of my reclaiming process is to convert the crumb-like, granular. non-coherent scrap, which is incapable of bein worked on a rubber mill, into a coherent tacky mass which can be converted into a smooth sheet immediately when being worked. My process described here'- in makes it possible to convert the crumb-like, granular scrap into a continuous sheet with relatively small force and consequently with the expenditure or a relatively small amountoi power and time. I

In the examples, the mixture is subjected to live steam pressure for different lengths of time which vary for different treating agents and different waste materials. The above examples show the times, temperatures and pressure which are used for the particular mixtures in question,

'but other combinations of times, temperatures and pressures are possible for other mixtures.

In the foregoing description and examples, I have described the novel processes to be employed in accordance with my invention in reclaiming fully or partly vulcanized or scorched materials .without reference to whether the scrap never contained fibers, or has been defibered, or still contains fibers from fabric or textile cords such as are usually found in commercial rubber scrap because the presence of fiber does not interfere with the action of the reclaiming substance. Accordingly, in the claims I do not limit myself to the treatment'or scrap which does not contain textile fibers.

Iclaim:

1. That step in the manufacture of reclaimed previously vulcanized rubbery synthetic polymers selected from the group consisting of polymers and copolymers of butadiene and chloroprene polymers and mixtures thereof which comprises heating such materials by contact with live steam in the presence ofthree to thirty-five percent of a saturated fatty acid having from six to eighteen carbon atoms and which does not contain hydroxyl group in the chain other than in the carboxyl groups and a solvent for the acid which swells the rubber.

2. A process according to claim 1 wherein the polymers are chloroprene polymers.

3. A process according to claim 1 wherein the polymers are butadiene polymers.

4. A proces according to claim fatty acid is stearic acid.

5. A process according fatty acid is laurlc acid.

6. A polychloroprene having been reclaimed by the process of claim 1, said reclaimed material being vulcanizable with sulphur.

7. A mixture of polychloroprene and butadiene polymers having been reclaimed by the process of claim 1, said reclaimed material being vulcanizable with sulphur.

- REE VlLMA LB BEAU.

REFERENCES crrEn The following references are of record in the file of this patent:

UNITED STATES PATENTS 1' wherein the Number Name Date 2,343,558 Kirby et a1 Mar. '1, 1944 2,324,980 Kilbourne July 20, 1943 2,280,484 Gumlich Apr. 21, 1942 2,273,506 Bachle Feb. 1'7, 1842 2,154,894 Essex Apr. 18, 1939 2,278,826 Castello et a1. Apr. 7, 1942 1,171,187 Glidden Feb, 8, 1916 Re. 2,206 McBurney Mar. 20, 1866 2,338,427 Gumlich Jan. 4, 1944 OTHER REFERENCES Chem. Ind., June 1942, p. 772.

to claim 1 wherein the 

